JPH10292018A - Polymer-dispersed polyol, polyurethane resin and production of polyurethane foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymer-dispersed polyol excellent in storage stability by feeding a hydrophilic monomer having a specified solubility in water and hydrophobic monomer in divided portions in the former and latter stages of polymerization and polymerizing them in the presence of a vinyl monomer and a radical initiator and to obtain a polyurethane foam excellent in hardness and resiliency. SOLUTION: A polyol such as polyester polyol or a polyether polyol and a monomer mixture containing at least one hydrophilic monomer having a water solubility of at least 10 pts.wt. per 100 pts.wt water at 20 deg.C under normal pressure are fed into a polymerizer and are stared to be polymerized at the decomposition temperature of the catalyst or above, desirably 60-200 deg.C in the presence of a radical polymerization initiator, a chain transfer agent and a dispersion stabilizer. In the latter stage of the polymerization, a monomer mixture containing at least one hydrophobic monomer having a water solubility of 0-5 pts.wt. per 100 pts.wt. water at 20 deg.C under normal pressure is added to the polymerizer, and the reaction mixture is polymerized to completion to obtain a polymer-dispersed polyol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a polymer-dispersed polyol and a method for producing a polyurethane resin and a polyurethane foam using the polymer-dispersed polyol produced by the method. By using the polymer-dispersed polyol of the present invention, a polyurethane foam excellent in durability such as wet heat compression set can be obtained.

[0002]

2. Description of the Related Art A polyol in which fine polymer particles obtained by polymerizing a vinyl monomer in a polyol are dispersed and conventionally called a polymer polyol or a polymer-dispersed polyol has been used as a raw material for polyurethane foams and polyurethane elastomers.

[0003] In particular, when a polymer-dispersed polyol is used for a flexible polyurethane foam, effects such as promotion of cell communication and improvement of foam hardness are obtained. In order to expect the effect of modifying polyurethane, it is preferable that the polymer to be dispersed has a high SP value that is significantly different from the SP value (solubility parameter) of polyurethane serving as a matrix, and acrylonitrile is mainly selected as a vinyl monomer. there were.

However, when acrylonitrile is used, there is a problem that the viscosity becomes high. In order to solve this problem, polymer-dispersed polyols obtained by copolymerizing styrene have been widely used. The use of styrene suppressed the rise in viscosity, and made it possible to produce a polymer-dispersed polyol having a high polymer concentration. From the viewpoint of the SP value, the interface between the polymer particles and the polyurethane matrix is more easily conformed, and the effect of improving the durability such as compression set is expected. However, in practice, in order to compensate for the decrease in foam hardness, since the polymer concentration in the polyol is increased or the amount of the polymer-dispersed polyol used is increased, the durability is not improved, but tends to deteriorate. .

With respect to comonomers other than styrene, JP-A-51-73588 discloses a copolymer characterized in that at least one of acrylonitrile and methacrylonitrile and at least one of acrylamide and methacrylamide are copolymerized. It teaches a method for producing a coalesced-polyol composition and a method for producing a polyurethane using the same. JP-A-52-997 teaches a method for producing a polymer-polyol composition characterized by radically polymerizing acrylonitrile and acrylamide in the coexistence of water, and a method for producing a polyurethane using the composition. ing. As described above, it is known that acrylamides are effective for lowering the viscosity of a polymer-polyol composition. However, in this case, not only the storage stability of the polymer-dispersed polyol itself is low because the dispersed polymer is hydrophilic,
It has been found that there is a problem that the storage stability of a resin solution in which water as a foaming agent, a catalyst, a foam stabilizer, and the like are mixed is poor, and that the polyurethane foam has poor wet heat compression set. However, if a hydrophilic monomer having a functional group capable of reacting with an isocyanate group in the molecule, such as acrylamides or hydroxyalkyl (meth) acrylate, is used as a comonomer, the hardness and rebound resilience of a polyurethane obtained from the polymer-dispersed polyol are obtained. The present inventors have confirmed that the physical properties such as the above are improved.

[0006] On the other hand, Japanese Patent Application Laid-Open No. 6-192347 discloses that a monomer having a different monomer composition ratio or monomer type is divided and fed, so that the polymer material is moved from the center to the surface of the polymer particles. Are presented. Specifically, it is described that since the particle diameter increases as the monomer is fed, the composition of the particle surface can be changed by changing the monomer composition ratio on the way. However, despite enumerating the monomers used in the present application, a method of changing the material of the polymer from the center to the surface of the polymer by focusing on the hydrophilicity and hydrophobicity of the monomer. Is not explicitly stated or suggested. For example, in Examples 1 and 2, only the concentration of styrene (corresponding to the hydrophobic monomer of the present invention) is changed between the first and second stages.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a polymer-dispersed polyol having good storage stability and a polyurethane foam having excellent properties such as hardness and rebound resilience and durability such as wet heat compression set. It is to provide a manufacturing method.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have used a hydrophilic monomer and a hydrophobic monomer in combination as essential components and divided them into a former stage and a latter stage of polymerization. It has been found that a polyurethane foam having improved durability such as wet heat compression set can be obtained by charging the foam.

That is, the gist of the present invention is to provide a method for producing a polymer-dispersed polyol by polymerizing a vinyl monomer in the presence of a radical initiator in the polyol, wherein the vinyl monomer is dissolved in water at 20 ° C. and normal pressure. A hydrophilic monomer (A) having a solubility of at least 10 parts by weight with respect to 100 parts by weight of water;
A hydrophobic monomer (B) having a solubility in water at 0 ° C. and normal pressure of 0 to 5 parts by weight with respect to 100 parts by weight of water, and all the hydrophilic monomers (A) used in the previous stage of polymerization are used. And a monomer mixture containing all the hydrophobic monomers (B) used in the latter stage of polymerization is charged, and polymerization is carried out, or all the hydrophobic monomers used in the first stage of polymerization are polymerized. A method for producing a polymer-dispersed polyol, comprising charging a monomer mixture containing (B), and charging and polymerizing a monomer mixture containing all the hydrophilic monomers (A) used in the latter stage of the polymerization. It is.
Further, the present invention provides a polyurethane resin produced by reacting an active hydrogen compound with a polyisocyanate, a method for producing a polyurethane resin, characterized by using the polymer-dispersed polyol obtained by the above method as the active hydrogen compound, And a polyurethane foam produced by reacting an active hydrogen compound and a polyisocyanate in the presence of a catalyst, a foaming agent, and a foam stabilizer, wherein the polyol containing the polymer-dispersed polyol obtained by the above method as the active hydrogen compound And a method for producing a polyurethane foam.

BEST MODE FOR CARRYING OUT THE INVENTION

Method for Producing Polymer-Dispersed Polyol Polyol As the polyol used in the present invention, polyether polyols, polyester polyols and the like which are usually used as raw materials for polyurethane can be used.

For example, monohydric alcohols such as methanol, butanol and allyl alcohol, water, ethylene glycol, diethylene glycol, propylene glycol,
Dipropylene glycol, dihydric alcohols such as 1,4-butanediol, glycerin, hexanetriol,
Polyhydric alcohols such as trimethylolpropane and pentaerythritol, saccharides such as sorbitol, sucrose, methylglucoside, dextrose, bisphenol A, bisphenol F, dihydroxybiphenyl, hydroquinone, resorcinol, phloroglucin, naphthalenediol, phenol formaldehyde condensate and the like Aromatic compounds, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, fatty acid amines such as ethylenediamine, hexamethylenediamine and diethylenetriamine, aromatics such as toluylenediamine, diphenylmethanediamine, naphthalenediamine, aminophenol and aminonaphthol A compound arbitrarily selected from the group consisting of amines is used as an initiator, usually with an alkali metal compound and an amine. Polyoxyalkylene polyols obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, 1,2-butylene oxide and styrene oxide using a catalyst such as a complex metal cyanide complex or at least one of No. Furthermore, a mixture of two or more arbitrarily selected from these polyoxyalkylene polyols can also be used.

Further, as the polyester polyol,
Polyhydric alcohols such as glycerin are used as initiators, and polyester polyols obtained by ring-opening addition of ε-caprolactone, γ-butyrolactone, etc., diols such as ethylene glycol, propylene glycol, pentanediol and terephthalic acid, phthalic anhydride, etc. And polyester polyols obtained by condensation with dicarboxylic acids or dicarboxylic esters such as dimethyl terephthalate.

Vinyl monomer The vinyl monomer of the present invention has at least one of 20 ° C.
A hydrophilic monomer (A) having a solubility in water at normal pressure of at least 10 parts by weight with respect to 100 parts by weight of water; 0 to 5 parts by weight of a hydrophobic monomer (B).

Examples of the hydrophilic monomer (A) include acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-methylacrylamide,
Acrylamide compounds such as -ethylacrylamide, N-isopropylacrylamide, acryloylmorpholine, diacetoneacrylamide, N, N-dimethylaminopropylacrylamide, acrylic acid, acrylic acid 2
-Hydroxyethyl, 2-hydroxypropyl acrylate, methacrylic acid, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, dimethylaminoethyl methacrylate and the like. Preferably,
Acrylamide compounds, especially acrylamide.

The hydrophobic monomer (B) includes styrene, α-methylstyrene, phenylstyrene, chlorostyrene, methyl acrylate, ethyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-stearyl acrylate, acrylic Tetrahydrofurfuryl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, methacrylic acid 2
-Ethylhexyl, octyl methacrylate, isodecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, cetyl methacrylate-stearyl, stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, methacrylonitrile , Vinyl acetate, vinyl chloride, vinylidene chloride and the like.
Preferred are styrene, methyl methacrylate, glycidyl methacrylate, butyl acrylate, especially styrene.

It is also possible to use a vinyl monomer (C) other than the above-mentioned hydrophilic monomer (A) and hydrophobic monomer (B), such as acrylonitrile, in combination.

The amount of the vinyl monomer used is 5 to 60% by weight, preferably 10 to 50% by weight, based on the total weight of the polyol and the vinyl monomer. If the amount of the vinyl monomer is less than 5% by weight, the effect of using the polymer-dispersed polyol, such as the hardness of the polyurethane, cannot be sufficiently improved. If the amount of the vinyl monomer exceeds 60% by weight, the viscosity of the resulting polymer-dispersed polyol increases significantly, and the dispersion stability also deteriorates.

Hydrophilic monomer (A) in vinyl monomer
Is preferably 5 to 80% by weight. If it is less than 5% by weight, the effect of improving the resin properties is small, and if it exceeds 80% by weight, the water absorption of the polymer-dispersed polyol obtained becomes high, and the storage of a resin liquid mixed with water as a foaming agent, a catalyst, a foam stabilizer and the like. Stability deteriorates.

Hydrophobic monomer (B) in vinyl monomer
Is preferably 5 to 90% by weight. If the amount is less than 5% by weight, the effect of lowering the viscosity and the effect of improving the durability are small.

Polymerization Initiator In the present invention, a radical initiator which generates a radical to initiate polymerization is usually used as the polymerization initiator. Specific examples include azo compounds such as 2,2'-azobisisobutyronitrile, peroxides such as benzoyl peroxide, and peroxydisulfide. The amount of the polymerization initiator to be used is generally 0.1 to 10.0% by weight, preferably 0.5 to 5.0% by weight, based on the vinyl monomer.

Chain Transfer Agent In the present invention, a chain transfer agent can be used if necessary. Examples include alcohols such as isopropanol, mercaptans, halogenated hydrocarbons, aliphatic tertiary amines, sodium methallylsulfonate, sodium allylsulfonate, and the like. The amount of the chain transfer agent used is 0.1 to 10.0% by weight based on the total weight of the polyol and the vinyl monomer.
Is preferred.

Dispersion Stabilizer Further, for the purpose of stably dispersing the polymer particles, it is possible to carry out polymerization in the presence of a dispersion stabilizer. Examples of such dispersion stabilizers include carbon-carbon unsaturated bond-containing polyester polyols described in JP-B-49-46556, and modified polyols having acryl, methacryl, allyl, etc. terminals at the terminals. No. In addition, high molecular weight polyoxyalkylene polyols and polyester polyols containing substantially no carbon-carbon unsaturated bond can also be used.

Solvent The polymerization reaction can be carried out without solvent, but can also be carried out in the presence of water and / or an organic solvent. Examples of the organic solvent include toluene, xylene, acetonitrile, hexane, heptane, dioxane, ethylene glycol dimethyl ether, N, N-dimethylformamide, butanol, isopropanol and the like.

Polymerization Reaction A polymerization reaction is carried out using the above polyol, vinyl monomer, polymerization initiator, and if necessary, a chain transfer agent, a dispersion stabilizer, a solvent, and the like, to produce a polymer-dispersed polyol. The polymerization reaction of the present invention can be carried out by a continuous system or a semi-batch system. A monomer mixture containing all the hydrophilic monomers (A) used in the first stage of the polymerization is charged, and a monomer mixture containing all the hydrophobic monomers (B) used in the second stage of the polymerization is charged to perform the polymerization. . Alternatively, a monomer mixture containing all the hydrophobic monomers (B) used in the first stage of the polymerization is charged, and a monomer mixture containing all the hydrophilic monomers (A) used in the second stage of the polymerization is charged. Polymerizes. More specifically, a hydrophilic monomer mixed solution and a hydrophobic monomer mixed solution are separately charged into a small amount of a polyol solution separately in the first and second stages of polymerization.

The polyol liquid is a part of the polyol to be used, and contains a chain transfer agent, a dispersion stabilizer and a solvent as necessary.

The hydrophilic monomer mixture comprises all the hydrophilic monomers (A), polyols and polymerization initiators to be used. If necessary, monomers (C) other than A and B, a chain transfer agent, and a dispersion stabilizer , A solvent. These may be charged at once as a mixed solution, or may be simultaneously charged in two or more series such as a monomer mixture (aqueous solution) and a polyol solution of an initiator.

The mixture of the hydrophobic monomers comprises all the hydrophobic monomers (B), polyols and polymerization initiators to be used, and if necessary, monomers (C) other than A and B, a chain transfer agent, and a dispersion stabilizer. , A solvent. These may be charged at once as a mixed solution, or may be simultaneously charged in two or more systems, such as a monomer mixture and a polyol solution of an initiator.

The polyol, the polymerization initiator, the chain transfer agent, the dispersion stabilizer, and the solvent, if necessary, can be divided into the former stage and the latter stage of the polymerization at an arbitrary ratio. It is preferable to be divided accordingly. Further, the polyol, the polymerization initiator, the chain transfer agent, the dispersion stabilizer, and the solvent used as needed may be the same or different before and after the polymerization.

The hydrophilic monomer mixture may be charged at the first stage and the hydrophobic monomer mixture may be charged at the second stage, or the hydrophobic monomer mixture may be charged at the first stage and the hydrophilic monomer mixture at the second stage. You may enter.

The polymerization temperature is determined according to the type of the catalyst, but is higher than the decomposition temperature of the catalyst, preferably 60 to 200 ° C.
More preferably, it is carried out at 80 to 160 ° C. Further, the polymerization reaction can be carried out both under pressure and under normal pressure. Before polymerization,
The polymerization conditions in the latter stage may be the same or different.

After completion of the polymerization reaction, the obtained polymer-dispersed polyol can be used as a raw material for polyurethane or the like as it is, but after unreacted monomers, decomposition products of a catalyst, a chain transfer agent, a solvent, etc. are distilled off under reduced pressure. Is preferred.

The concentration of the vinyl polymer contained in the polymer-dispersed polyol of the present invention is 5 to 60% by weight based on the obtained polymer-dispersed polyol.

The average particle size of the vinyl polymer contained in the polymer-dispersed polyol of the present invention is preferably from 0.01 to 10 μm from the viewpoint of the dispersion stability of the vinyl polymer and the effect on the physical properties of the polyurethane foam.
Such a particle size can be achieved by appropriately adjusting the type and amount of the chain transfer agent, the dispersion stabilizer, the solvent, the weight composition ratio of the monomers, and the like.

Polyurethane Resin The polyurethane resin of the present invention is obtained by reacting a polyol containing the above-mentioned polymer-dispersed polyol as an active hydrogen compound with a polyisocyanate, if necessary, in the presence of a catalyst and other auxiliaries. .

Polyurethane Foam The polyurethane foam of the present invention comprises a polyol containing the above polymer-dispersed polyol as an active hydrogen compound and a polyisocyanate, a foaming agent such as water, a catalyst, a foam stabilizer such as an organosilicon surfactant, and if necessary. , A cross-linking agent, a plasticizer, a colorant, and other auxiliaries.

Active Hydrogen Compound As the active hydrogen compound, a polyol containing the polymer-dispersed polyol of the present invention is used. A mixture of one or more of the polymer-dispersed polyol of the present invention, a mixture of the polymer-dispersed polyol of the present invention and a polymer-dispersed polyol produced by a conventional technique, a mixture of the polymer-dispersed polyol of the present invention and the polyol described above, the present invention; And a mixture of a polymer-dispersed polyol of the formula (I), a polymer-dispersed polyol produced by a conventional technique, and the above-mentioned polyol.

Polyisocyanate As the polyisocyanate, there can be used known ones used for producing polyurethanes such as aromatic, aliphatic and alicyclic groups having two or more isocyanate groups in one molecule. For example, 2,4-tolylene diisocyanate,
2,6-tolylene diisocyanate, 80/20 weight ratio of these organic polyisocyanates (TDI-80 / 2
0), isomer mixture at 65/35 weight ratio (TDI-65 / 35), crude tolylene diisocyanate containing polyfunctional tar (polyfunctional tar is a by-product of isocyanate production, A mixture of tar-like substances containing two or more groups in the molecule. The same applies hereinafter.), 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate,
2,2′-diphenylmethane diisocyanate, any isomer mixture of diphenylmethane diisocyanate, 3
Crude diphenylmethane diisocyanate (polymeric MDI) containing core or higher polyfunctional tar, toluylene diisocyanate, xylylene diisocyanate,
Hexamethylene diisocyanate, isophorone diisocyanate, naphthalene diisocyanate, paraphenylene diisocyanate, norbornene diisocyanate and carbodiimide modified or buret modified products of these organic polyisocyanates, or prepolymers obtained by modifying these with polyols or monools alone or in combination. Is mentioned. The above polyisocyanate compounds can be used in a mixture at an arbitrary ratio.

In producing the polyurethane resin and the polyurethane foam, the equivalent of the free isocyanate group in the polyisocyanate compound to the equivalent of the active hydrogen group in the active hydrogen compound such as a polyol containing a polymer-dispersed polyol, water and a crosslinking agent is used. The isocyanate index (hereinafter, abbreviated as NCOindex) as a ratio is 0.1.
The range of 50 to 2.0 is preferred.

Catalysts As the catalyst, all those usually used in the production of polyurethane can be used. For example, amine catalysts include triethylamine, tripropylamine, tributylamine, N, N, N ', N'-tetramethylhexamethylenediamine, N-methylmorpholine, N-ethylmorpholine, dimethylcyclohexylamine, bis [2 −
(Dimethylamino) ethyl] ether, amine salts such as dibutylamine-2-ethylhexoate such as salts of triethylenediamine and triethylenediamine, and organometallic catalysts such as tin acetate, tin octylate, tin oleate and lauryl Examples include tin acid, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, tin 2-ethylhexylate, lead octanoate, lead naphthenate, nickel naphthenate, and cobalt naphthenate. These catalysts can be arbitrarily mixed and used in an amount of 0.0001 to 1 with respect to 100 parts by weight of the active hydrogen compound.
0.0 parts by weight.

Foaming agents Foaming agents include water, trichloromonofluoromethane, dichlorodifluoromethane, 2,2-dichloro-1,1,1-
One or a mixture of two or more of trifluoroethane, 1,1-dichloro-1-fluoroethane, methylene chloride, trichlorotrifluoroethane, dibromotetrafluoroethane, trichloroethane, pentane, hexane and the like.

Foam stabilizer A foam stabilizer is a conventionally known organic silicon-based surfactant, for example, L-520, L-532, L-520 manufactured by Nippon Unicar Co., Ltd.
540, L-544, L-550, L-3600, L-
3601, L-5305, L-5307, L-5309
Toray Dow Corning SRX-253, SR
X-274C, SF-2961, SF-2962, etc., Shin-Etsu Silicone F-114, F-121, F-12
2, F-220, F-230, F-258, F-260
B, F-317, F-341, F-601, F-606
TFA-4200, TFA- manufactured by Toshiba Silicone Co., Ltd.
4202 and the like. These foam stabilizers can be arbitrarily mixed and used, and the amount is 0.1 to 10 parts by weight based on 100 parts by weight of the active hydrogen compound.

Crosslinking Agents Crosslinking agents include polyols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,3-butanediol and 1,4-butanediol, and alkanolamines such as triethanolamine and diethanolamine. , Ethylenediamine, diethylenetriamine, aliphatic polyamines such as triethylenetetramine, aniline, 2,4-tolylenediamine, aromatic polyamines such as 2,6-tolylenediamine, and ethylene oxide, propylene oxide and the like to these active hydrogen compounds. It is a compound having a hydroxyl value of 200 mgKOH / g or more obtained by addition. In addition, a hydroxyl value of 200 m obtained by adding ethylene oxide, propylene oxide, etc. to hydroquinone, resorcin, etc.
Compounds of gKOH / g or more can also be used.

Method for Producing Polyurethane Resin A polyol containing the above-mentioned polymer-dispersed polyol, a catalyst, other auxiliaries, and a polyisocyanate adjusted to a predetermined NCOindex are weighed, mixed with stirring, and then defoamed under reduced pressure. The reaction solution is heated to a predetermined temperature, for example, 30 to
It is poured into a mold whose temperature has been adjusted to 100 ° C., and is heated in an oven at a predetermined temperature, for example, 60 to 200 ° C. for a predetermined time, for example, 1
After curing for ~ 3 days, the desired polyurethane resin is obtained by releasing the polyurethane resin.

Method for Producing Polyurethane Foam A resin solution is prepared by mixing a predetermined amount of a polyol containing the above-mentioned polymer-dispersed polyol, a foaming agent, a catalyst, a foam stabilizer and other auxiliaries, and is prepared at a predetermined temperature, for example, 20 to 30 ° C. Adjust to The polyisocyanate is converted to the specified NCO
weighed according to x, at a predetermined temperature, for example, 20-30 ° C
Adjust to Thereafter, the resin solution and the polyisocyanate are rapidly mixed to perform free foaming, or poured into a mold whose temperature is controlled to a predetermined temperature, for example, 30 to 70 ° C. In the case of injection molding in a mold, the reaction solution is foamed and filled in the mold, and then, if necessary, at a predetermined temperature, for example, 60 to 200 ° C.
Cured for a predetermined time, for example, 1 to 20 minutes in an oven,
The polyurethane foam is demolded, and if necessary, the foam is crushed to open the cells to obtain a desired polyurethane foam.

[0045]

EXAMPLES Examples of the present invention will be shown below to clarify aspects of the present invention, but the present invention is not limited to these examples. Raw materials, abbreviations, and analysis methods used in Examples and Comparative Examples are described below. Polyol A; hydroxyl value 3 obtained by addition polymerization of glycerin with propylene oxide and then ethylene oxide
4 mg KOH / g, polyoxyethylene oxypropylene triol having an ethylene oxide content of 14% by weight Polyol B; a hydroxyl value of 30 mg obtained by adding propylene oxide to a reaction product of polyol A and maleic anhydride
KOH / g polyetherester polyol AN; acrylonitrile St; styrene AAM; acrylamide HEMA; 2-hydroxyethyl methacrylate water; ion-exchanged water IPA; isopropanol AIBN; azobisisobutyronitrile viscosity; . Particle size: The volume average particle size is measured using a particle analyzer COULTER LS230. Polyisocyanate A; polymeric MDI (NCO%
= 31.3%, manufactured by Mitsui Toatsu Chemicals Co., Ltd. Catalyst A; 16.5% by weight of diethylene glycol solution of triethylenediamine Hardness of polyurethane resin; Surface of cylindrical sample using type A durometer described in JIS K7215 Measure hardness. Rebound resilience of polyurethane resin: The rebound resilience of a cylindrical sample is measured using a Lupke rebound resilience tester described in JIS K6301. Crosslinking agent: KL-210 (hydroxyl value 830 mgKOH / g
Amine-based crosslinking agent, manufactured by Mitsui Toatsu Chemical Co., Ltd.) Catalyst B; Minico L-1020 (amine-based catalyst,
Catalyst C; Niax A-1 (amine-based catalyst, manufactured by ARCO) Foam stabilizer; SRX-274C (silicone foam stabilizer, manufactured by Toray Industries, Inc.)
Dow Corning Co.) Polyisocyanate B; TM-20 (80 parts by weight of a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate in an 80:20 weight ratio and Polymeric M)
Polyisocyanate mixture consisting of 20 parts of DI, manufactured by Mitsui Toatsu Chemicals, Inc.) Foam physical properties: Measured in accordance with JIS K6401 and K6402.

1. Production of Polymer Dispersed Polyol Examples 1 to 4 20 parts by weight of polyol A was charged into a polymerization tank equipped with a temperature controller, a stirrer, a liquid feeder, and a condenser, and the temperature was raised to 100 ° C. while stirring. The first-stage feed solution previously mixed at the composition ratio shown in Table 1 was charged at a uniform speed over 1 hour, and then the second-stage feed solution was charged at a uniform speed over 1 hour. went. After completion of the reaction, unreacted monomer, solvent, initiator, decomposition product of
The polymer was removed at 120 ° C. under a reduced pressure of 65 Pa (5 mmHg) to obtain polymer-dispersed polyols A to D shown in Table 1. In order to evaluate the performance of the obtained polymer-dispersed polyol, a polyurethane resin was produced by the following method. 100 g of polymer-dispersed polyols A to D are weighed into a 500 ml polycup, and 0.03 g of catalyst A and NCOindex
1.00 isocyanate A and a stirrer (3
(00 rpm) for 3 minutes, and the mixture was defoamed under reduced pressure for 15 minutes. The mixture was poured into an aluminum mold (cylindrical mold having a diameter of 30 mm and a depth of 12 mm) kept at 80 ° C. in advance, cured at 80 ° C. for 48 hours in a nitrogen atmosphere, and then released to obtain a polyurethane resin. Table 1 shows the properties of the polymer-dispersed polyol and the physical properties of the polyurethane resin.

[0047]

[Table 1]

Comparative Examples 1 to 3 In the same manner as in Examples 1 to 4, a feed solution previously mixed with the composition shown in Table 2 was charged at a uniform speed over 2 hours.
The aging reaction was performed for 1 hour as it was. After the completion of the reaction, unreacted monomers and the like were removed in the same manner as in Examples 1 to 4, and polymer-dispersed polyols EG were obtained. Polyurethane resins were prepared in the same manner as in Examples 1 to 4, and evaluated. Table 2 shows the properties of the polymer-dispersed polyol and the physical properties of the polyurethane resin.

[0049]

[Table 2]

2. Production of Polyurethane Foam Examples 5 to 8, Comparative Examples 4 to 6 A resin solution was prepared by mixing the following seven components,
The temperature was adjusted to Polyol A 50 parts Polymer-dispersed polyol 50 parts Crosslinking agent 3.0 parts Water 3.4 parts Catalyst B 0.4 parts Catalyst C 0.1 parts Foam stabilizer 1.0 parts Polyisocyanate B so as to have NCOindex 1.05 It was weighed and temperature adjusted to 23 ° C. The above resin solution and polyisocyanate B are mixed with rapid stirring for 6 seconds, and then poured into an aluminum mold having an internal dimension (length: width: depth) ratio of 4: 4: 1 which has been previously adjusted to 60 ° C. The lid was closed and foamed. After heating and curing in a hot air oven at 100 ° C. for 5 minutes, the foam is removed from the mold,
Crushed. Tables 3 and 4 show the physical properties of the obtained foam.

[0051]

[Table 3]

[0052]

[Table 4]

From the results of Examples 1 to 4 and Comparative Examples 1 to 3,
It can be seen that when a hydrophilic monomer such as acrylamide or 2-hydroxyethyl methacrylate is used as a comonomer as compared with a conventional acrylonitrile-based polymer polyol, the hardness and resilience of the polyurethane resin are improved. Also, from the results of Examples 5 to 8 and Comparative Examples 4 and 6, the wet heat compression set of the polyurethane foam is greatly improved by separately charging the hydrophilic monomer and the hydrophobic monomer in the first and second stages of the polymerization. It can be seen that a polymer-dispersed polyol is obtained.

[0054]

As described in detail above, according to the production method of the present invention, a polymer-dispersed polyol capable of providing a polyurethane resin having improved hardness, rebound resilience and the like and a polyurethane foam having greatly improved wet heat compression set can be obtained. .

Continuation of the front page (51) Int.Cl. ⁶ Identification code FI C08L 71/02 C08L 71/02 // (C08G 18/63 101: 00) (72) Inventor Masahiro Isobe 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Kazuhiko Okubo 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Mitsui Toatsu Chemical Co., Ltd.

Claims (6)

[Claims] 1. A method for producing a polymer-dispersed polyol by polymerizing a vinyl monomer in the presence of a radical initiator in a polyol, wherein the vinyl monomer has a solubility in water of at least one kind at 20 ° C. and normal pressure of 100 wt. At least 1 part
0 parts by weight of a hydrophilic monomer (A) and at least one kind of a hydrophobic monomer (B) having a solubility in water at 20 ° C. and normal pressure of 0 to 5 parts by weight with respect to 100 parts by weight of water. A monomer mixture containing all the hydrophilic monomers (A) used in the first stage of the polymerization, and a monomer mixture containing all the hydrophobic monomers (B) used in the second stage of the polymerization. A monomer mixture containing all the hydrophobic monomers (B) used in the first stage of the polymerization is charged, and a monomer mixture containing all the hydrophilic monomers (A) used in the second stage of the polymerization is charged. A method for producing a polymer-dispersed polyol, comprising charging and polymerizing. 2. The hydrophilic monomer (A) is at least one monomer selected from acrylamide compounds, (meth) acrylic acid, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and dimethylaminoethyl methacrylate. The method for producing a polymer-dispersed polyol according to claim 1. 3. The method for producing a polymer-dispersed polyol according to claim 1, wherein the hydrophilic monomer (A) comprises at least one acrylamide compound. 4. The process for producing a polymer-dispersed polyol according to claim 1, wherein the hydrophobic monomer (B) comprises at least one monomer selected from styrene, methyl methacrylate, glycidyl methacrylate, and butyl acrylate. . 5. A polyurethane resin produced by reacting an active hydrogen compound with a polyisocyanate, wherein the polymer-dispersed polyol obtained by the method according to claim 1 is used as the active hydrogen compound. Method. 6. A polyurethane foam produced by reacting an active hydrogen compound with a polyisocyanate in the presence of a catalyst, a foaming agent and a foam stabilizer, obtained by the method according to claim 1 as an active hydrogen compound. A method for producing a polyurethane foam, comprising using a polyol containing a polymer-dispersed polyol.